Selective adsorbent char for separation of straight chain from nonstraight chain hydrocarbons



INVENTOR ATTORNEY July 5, 1960- R. B. MASON SELECTIVE ADSORBENT CHAR FOR SEPARATION OF STRAIGHT CHAIN FROM NON-STRAIGHT CHAIN HYDROCARBONS Filed Sept. 5, 1957 Y YB 2 4 P R RL 2 2 W W W AIFWH HTAI w P m w R O M MW 0 E T L 2 M ME 4. ov a 8 RE I 6 EFL FIGURE FIGURE 2 VAPOR HEATING JACKET RALPH B. MASON BYW 045 12 United States.

SELECTIVE ADSORBENT CHAR FOR SEPARA- TION OF STRAIGHT CHAIN FROM NON- CHAIN HYDROCARBONS '6 Claims. or. 252-421 The present invention relates to an improved selectent tive adsorbent for the separation of hydrocarbons, and

particularly straight chain hydrocarbons from. branch chain and cyclic hydrocarbons. Moreparticularly, it relates to an adsorbent, and a method for preparing an adsorbent, which has the property of separating narrowly boiling hydrocarbons into straight chain compounds and other types, such as branch chain and cyclic compounds by selectively adsorbing the normal paraflin and olefins. QIt is well known in the art that an activated carbon useful in hydrocarbons separations may be made by steaming carbon from various sources, such as wood charcoal, coconut shells, petroleum chars and the like. Activated carbons made in this manner have some selectivity for separation of straight chain hydrocarbons. Activated carbons made in this manner have some selectivity for the separation of straight chain hydrocarbons from branch chain isomers, but theselectivity is too low for .commercial application of such separation processes. It is highly desirable to make these separations, in particular, to remove straight chain, low octane hydrocarbons from naphtha streams boiling in the gasoline boiling range. Removal of these components from, say, virgin or catalytic naphtha results in the substantial upgrading of these fractions.

According to the present invention, it has been found sections of the system also is a severe handicap to efficient heat inputand renders the rapid and economical withdrawal of the product an impossibility. Thus the difiicultiesin charring in a conventional system are threefold, i.e. (1) hazardous, (2) results in impure product due to solidification in hot and cold sections of they system, and (3) uneconomical due to problems associated with handling the product and-to methods of heating. Furthermore,. the final product, though having excellent adsorptive characteristics, showed no particular selectivity fornormal hydrocarbons over non-normals.

In brief compass, in accordance with the present invention, a polyvinylidene chloride, such as Saran supplied by the Dow Chemical Company, is heated insuspension in a suitable liquid to a temperature of about 400 to 700 F the liquid having a similarboiling range.

This permits dehydrochlorination over conditions where" volume expansion is near maximum. Following the partial dehydrochlorination and setting of the plastic, the solvent is removed by settling, and/or filtration,-and, if

desired, subjected to further pyrolysis in the presence of;

an inert. stripping gas to sweep'out liberated HCl.

. The process of the present invention will be better understoodwhen read in conjunction with the accompanying drawing, which is a flow plan of a preferred embodiment thereof. I

Turning now to the drawing, solvent for the process is passed through line 2 to preheater 4 and heated to a temperature of about 400 to 700 F. A suitable solvent is a light, highly refined mineral oil having a kinematic viscosity of about 0.2 to 2 centistokes at the operating temperature; other solvents that may be employed are aromatics, silicone polymers, molten metals, molten salts, and the like. The'resinis added via'hopper 5 and the mixture passed into heating-soaking ves- Sci 10. Temperatures here are maintained in the range a of 400 to 700 F., preferably 450 to 600 F.; suitthat certain synhetic resins, and particularly polymers of vinylidene chloride, when charred and activated by the process of the present invention, produce active chars possessing these selective adsorption characteristics to a marked degree. These same resins, however, when charred in a manner not within the scope of the present invention, do not produce chars with these selective adsorption characteristics.

When it was attempted to prepare chars from polyvinylidene chloride by heating the material, considerable difliculties were encountered. Difliculties encountered in the charring of polyvinylidene chloride can be appreciated upon consideration of such polymers. They are thermoplastic, i.e.. soften, and can be molded upon the application of heat. Upon the elevation of the temperature to a valuein the range of 300 to 400 F., hydrogen chloride is evolved. This gas evolution, together with the plastic characteristic mentioned, produces a plastic, putty-like mass with an enormous volume expansion. This enlargement has been observed to be Also, a sizeable portion of the product is.

able heating means such as fired coils, steam lines and the like may be employed. A residence time of 30 to 60 minutes is desirable. Liberated HCl is removed through line 11.

Due to the liquid heating medium, excellent temperature control may be maintained during the critical period when the resin is initially charred and normally goes through a semi-plastic, tacky stage, at which stage it is extremely difiicult to manage. As discussed previously, this sticky, semi-plastic state is due to the thermoplastic 'nature of the resin and the difiiculties are increased by the expansion due to hydrogen chloride evolution. It has been observed that these difiiculties are'further removed by addition of the resin to the liquid in small increments or continuously so that the initial volume expansion is efiected immediately and because of the size of the charge does not reach unmanageable dimensions.

The partially decomposedand expanded product, especially when the decomposition is accompanied with agitation,'is finely divided segregated particles amenable to filtration and subsequentextraction orstripping'of the solvent.

The semi-charred resin is now passed via line 12 to separator 14 where, by settling and/or filtration, the solvent is withdrawn through line 16 and may be recycled. The product char is passed through line 18 to vessel 20 where residual solvent is removed by stripping with steam admitted through line 24. Alternatively, an auxiliary solvent such as benzene, naphtha hydrocarbons, chloroform, acetone or the like may be used to remove adhering solvent.

Final pyrolysis is carried outin vessel 26. Here the char is heated to 1000 to 2000 F., preferably 1400" to 1800 F. Heat for this is supplied by any convenient means. A suitable method consists in direct firing with solid such as sand, metallic sal't'andthe like; 011

, illustrated by the following specific examples:

. peration'was Nn m F.) [47 grams of polyvinylidene chloride were-addedfwi-th v I two inter 'flask equipped with a reflux COIIdeIiS stirrer served as the reactor. Although the decomposi vessel 26ers relatively small diameter tubes '(6 inch eter and less); Other methods consist in indirect heating with the reactor tubes passing through a heated fluidized .-hed such as sand, spent cracking catalyst and itherlike.

Still other methods consist in heat tf'afnsfffibnr rt separation of the char from the 'solidijeliitriat o vent extraction or by' some suitable means. The-final pyrolysis'step' is also preferablycarried' but the presence of aninertgas, 'such a's nitrogen, introduced thiouglrlifie 28 to sweep out further liberated HCl; The finished char is withdrawn th'rough line -30 and is ow readfiwithout steam activation to out the sel uinea previously.-

' r The process argues emf invention niajl .in many'details. Theprocess is-not limited to operation .With polyvinylidene chloride polymers although a Whole number mole ratio (insertion to; Volatile gaseous corn poundis quite desirous. Thiis',-ffbr example, polyvinylicarbon containing compound having a stable material evolved as a gas is not peculiar tothe chloro hydrocarbons; It' is to -be -found4n the -'carbohydrate molecules, including starch and cellulose structures. "With such ma 't'e'rials water is evolved upon pyrolysis leaving carbon.

Althoughcharring of suchmatenials is described inprior art, the altered-performance obtained .upon pyrolyzing in the pres'ence of a liquid suspendantpermits the use of such.

materials in placeof or mixed with the chloro compounds mentioned as a f eed to eharringoperation.

f Thepr'ocess of' the present invention may be -EXAMPLE1 Polyvinylidene chloride was i charred with diificulty in separate experiments usinga VycorT"reactor at'temperatures of 1000",.1200" and 1400-F, with theperio'ds'on temperature heingin 'therange of-fori'e to two hours. The

- charges'of 202 1 grams were heated "with nitrogen flow to initial decomposition temperature of ahou't 350 to 400 F.

- wherethe'voluine expansionnecessitated stoppageof the gas flow and in 'someinstahces renioval of part ofthe charge. Only the material remaining in the heated' 'z one was'empl'oyed' in subsequent tests.- Dueto*s't'opiziag'e'sin the exit lines the continuation of the'charrin'gwas 'in the absence of purge gas fandthe evolved gas was'backd out through the inlet orthrough a cOnnection-ini rOVisedat the entrancerof thetherrnocouple V I 'difiiculties encountered in the previousi' lifii'inifit's wereovercoriie by conducting'thejinitialfdeco position stirring in fsmall increments over, a'30'r'ninute period, A

tion was essentiallycomplete upon completion of theaddition the product waskept on heat for fou'r'hour'sL The partially decomposedfproduct was filtered and was then extracted with enz'enem Soxhlet equi ment to remove the residual Nujol. Ther'eniaining' product was heated a slow stream of nitrogen (10 cc./ min.) 'frhhrambient te'in 1 turefl-to 1450 F.;andjfor two hours'at -1450' F. As a result of "the initial treatment no diificlilty Was experieheedin'this final 'h'eattreatm'ent. This is in'marked eadsorption; def

further I contrast to the charring operation in the same equipment without the initial decomposition in the presence. of an pendant.-

In other experiments the product from this and asimilar decomposition in Nujol but at 400 F. were given final decomposition treatments of 600 "F. and 1650 addition to the i450 F. treatment described above V Chars btained pyrite recess of Exempt d an ample 2 were examinedier :=adscrptioh characteristicsy V 'Iheir'adsonptive properties towards purenheptane 2 methylpentane were determined by measiiremefits ilfa laboratory-apparatus designedfor adsorption studies. V A

sketch of the equipmehtis' shown'in Figurel. Thechar 7 sample is weighed -(ab't nit lliS gram.) into its container-,

inserted into the apparatus as shown and the system is.

evacuated. Mercury is then-allowed into the reservoir" at "the Bottom allowed isreach temperature Jane .the,

7 through thefi iti "Afterthejsystem equilibratesth pres height difiiftintil 'betweenfthe tnercury lever-above the reservoir and the revel in 'ithe "tube; to'tnevacnumpump allf-me-asured amount {of adso'rbate (n hep noted. A tane, etc.')'

pette'dirito thesampl'e' syste'm by touching the tip of thepipette to the mercuryseal ed'glass;frit above the sample, the vacuum system drawin'g'the adsorbate;

sure is' 'read onc'e again; This procedure is 'repeiatediin about 500 Hg pressure existsin the sample system.

From the known volume of the sample container the mercury reservoir, the size of'the adsorbent sample taken and the prcssure adsorb'ate relationships the adsor tion capacity is determined directly;

By such measurements it has been observed that the t chars prepared by initial decomposition in aliquid s'u's' drocarbbnaceous .compdsition wh'erein the ratioof V gen to '6hlori'1ieat'o1ns isi lzlaandlwhich evolves onpYfoly'sis a"hydr 6gen;chloride comprising gastofa to suspended-inn li'iquid-havinga. boiling Zpoint within pendant is selective for normal parajtfin hydrocarbons j and rejects to a major extent branched'chain parafiins;

Data showing are: 7

' .Adso'fptibn'ofpolyvinylideiz'e chloride ch rs I Pyrolysis ."Pr'etreatment Temp, r F. n-Heptane 2-Ms' Toluene Pntane a 1. An improved process fcrpreparing a selective hd-i soibent char having uniform i'pores adapted to adsorb straight-chainhydrocarbonsend reject non-straightchain hydrocarbons, which comprises heating a chlorinated hy peratui'e jin the. range of about to 700 f said hydriicarbonac'eoiis material. in jsaid liquid, has,

earning 'a "res "ce time of "fromf30 niinutes re r'novingfsaid'cliarred'material-from 'said, liquid, thereafter hatiiig' 'charrfedniaterial to a temperature of about 1'000 to 2000 1 {and-recovering a superic irg-selec tiiiead'sorheiitchar.

sofbe'nt c'ha'r which comprises heatingf' a suspension oif polyvinylide'rie ehloride in "an 'organicliquid having a boilin point 'Within'fth'e range of ssumes to '-7'(i0 F. at a temperatu e of 400 -to 700 F., maintaining'a residence time of from 30th 60. minutes 'in-said -liquid, separating said liquid from" char, and rui'therf heating said impfoved process for. preparing a selective ads char at a temperature of 1000 to 2000 F. in the presence of an inert gas.

3. The process of claim 2 wherein said liquid is a light, highly refined mineral oil having a kinematic viscosity of 0.2 to 2 centistokes.

4. The process of claim 2 wherein said initial charring temperature is in the range of 450 to 600 F. and the final pyrolysis temperature is about 1400 to 1800" F.

5. The process of claim 2 wherein said polymer is continuously added in small increments to said liquid.

6. A selective adsorbent char having the property of adsorbing straight chain hydrocarbons and rejecting branched chain hydrocarbons prepared by suspending polyvinylidene chloride in a highly refined mineral oil having a kinematic visco'sity of from about 0.2 to 2 centistokes, heating said suspension for 30 to 60 minutes at 450 to 600 F., removing charred material from said liquid and further heating said charred material in the presence of an inert gas at a temperature of 1400 to 1800 F.

References Cited in the file of this patent UNITED STATES PATENTS 1,442,372 Wallerstein Jan. 16, 1923 1,499,908 Chaney July 1, 1924 1,563,295 Sauer Nov. 24, 1925 2,609,256 Baker et a1. Sept. 2, 1952 2,736,642 Baker et al Feb. 28, 1956 FOREIGN PATENTS 262,278 Great Britain Dec. 9, 1926 412,209 Great Britain, June 18, 1934 802,765 France June 13, 1936 

1. AN IMPROVED PROCESS FOR PREPARING A SELECTIVE ADSORBENT CHAR HAVING UNIFORM PORES ADAPTED TO ADSORB STRAIGHT CHAIN HYDROCARBONS AND REJECT NON-STRAIGHT CHAIN HYDROCARBONS, WHICH COMPRISES HEATING A CHLORINATED HYDROCARBONACEOUS COMPOSITION WHEREIN THE RATIO OF HYDROGEN TO CHLORINE ATOMS IS 1:1 AND WHICH EVOLVES ON PYROLYSIS A HYDROGEN CHLORIDE COMPRISING GAS TO A TEMPERATURE IN THE RANGE OF ABOUT 400* TO 700*F. WHILE SUSPENDED IN A LIQUID HAVING A BOILING POINT WITHIN THE RANGE OF APPROXIMATELY 400* TO 700* F, PARTIALLY CHARRING SAID HYDROCARBONACEOUS MATERIAL IN SAID LIQUID, MAINTAINING A RESIDENCE TIME OF FROM 30 TO 60 MINUTES, REMOVING SAID CHARRED MATERIAL FROM SAID LIQUID, THEREAFTER HEATING SAID CHARRED MATERIAL TO A TEMPERATURE OF FROM ABOUT 1000* TO 2000*F. AND RECOVERING A SUPERIOR SELECTIVE ADSORBENT CHAR. 